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Wednesday, August 10, 2011

Gulf Plume Makeup Determined

During the Deepwater well
disaster, the most dramatic effect after the fire itself was the persistence of
a plume deep in the water.Now it turns
out that plume represented only two percent of oil flow and consisted of the soluble
fraction referred to as BTEX.The
remaining oil has been consumed by evaporation and ongoing biological degradation.

We can also presume that the BTEX
fraction which appears to be dilute enough to cause no lasting problem is also
been biologically degraded.This really
needs to be confirmed although it certainly looks good.

The good news is that Mother
Nature is able to handle a massive oil spill in tropical conditions to a large
extent quite quickly.That does not make
the experience pleasant but we have to take it.

The good news is that we are
entering the last decade of the Age of oil.Good ri9ddence although I have plenty of family and friends who will
lament its end.

Taking another major step in sleuthing the 2010 Deepwater Horizon oil spill,
a research team led by the Woods Hole Oceanographic Institution (WHOI)
determined what chemicals were contained in a deep, hydrocarbon-containing plume.

The plume was at least 22 miles long.

The scientists mapped and sampled it last summer in the Gulf of Mexico; it was a residue of the Deepwater
Horizon oil spill.

The researchers took a major step in explaining why some chemicals, but
not others, made their way into the plume, they report this week in the online
edition of the journal Proceedings of the NationalAcademy
of Sciences.

The National Science Foundation (NSF) funded the project through three
Rapid Response Research grants, which enable support for fast-response research
tied to events such as the Gulf oil spill.

"By any measure, this is a remarkable study," says Don Rice,
director of NSF's chemical oceanography program. "Reddy and colleagues add
several critical tiles to the growing Deepwater Horizon mosaic. We now have
hints of why some earlier studies appear to refute one another.

"Most importantly," says Rice, "we now have a far better
understanding of how and why an oil 'spill' into the ocean from below differs
from one from above. The significance of this work extends well beyond the Gulf of Mexico."

It "helps explain and sheds light on the plume formation, and
verifies much of what we thought about the plume's composition," said WHOI
chemist Christopher Reddy, lead author of the study.

The data "provide compelling evidence" that the oil
component of the plume sampled in June 2010 essentially comprised benzene,
toluene, ethybenzene, and total xylenes--together, called BTEX--at
concentrations of about 70 micrograms per liter, the researchers reported.

The BTEX concentrations in the plume were "significantly higher
than background," Reddy said. "We don't know with certainty the adverse
effects it might cause on marine life."

WHOI scientist Judith McDowell said that acute toxicity levels of BTEX
are in the range of 5 to 50 milligrams per liter for aquatic organisms--100 to
1,000 times greater than that observed in the plume.

Sublethal effects, including neurological impairment, are observed at
lower levels, she said.

"In most instances the BTEX compounds are volatilized very
quickly, such that exposure duration is very short," McDowell said.
"The persistence of BTEX at depth poses an interesting question as to the
potential effects of these compounds on mid-water organisms."

A critical component of the study was a one-of-a-kind fluid sample the
team collected directly from the broken riser at the Macondo well.

To accomplish this, the team used an isobaric gas-tight sampler, a
unique piece of equipment developed by WHOI geochemist Jeff Seewald and his
colleagues, and intended for use collecting fluids from deep-sea hydrothermal
vents.

With the gas-tight sampler and other necessary equipment, the lead
scientists were shuttled from their active research vessel to a smaller boat
and brought to the Ocean Intervention III, operating above the Macondo well.

They were then given 12 hours--working with many unknowns--to do
something never done before.

Using an oil industry remotely
operated vehicle, they maneuvered the gas-tight sampler to the source of the
spill to capture an "end-member" sample of fluid as it exited the
riser pipe.

No other such sample exists.

By analyzing this sample, the scientists were able to determine what
was in fluid spewing from the Macondo well before nature had a chance to
weather it and the exact ratio of gas and oil in the fluid.

"Getting this sample was probably the most dramatic and thrilling
thing I have done in my life," Reddy said.

Using petroleum industry terms, they found a gas-to-oil ratio (GOR) of
1,600 cubic feet of gas per barrel of oil. This value is smaller than other
proposed values, Reddy said, suggesting "more oil may have been coming out
of the well than other people calculated."

Analyzing samples from the Macondo well and those they collected from
the plume in June 2010 aboard the research vessel Endeavor, the researchers
found that BTEX represented about 2 percent of the oil that came out of the
well, but "nearly 100 percent of what was in the plume," Reddy said.

"A small, selective group of compounds took a right-hand
turn" after exiting the well and formed the 3,000-foot-deep plume, he
added.

This raises a number of questions, he said, including, "Why are
those chemical there in those concentrations? Why are they so abundant in the
water?"

The answers have to do with the tendency of those chemicals that
"like" to dissolve in water to migrate to the plume, Reddy said.

Unlike other substances emanating from the well that degrade or evaporate
in the water or at the surface, the compounds in the plume showed little
evidence of biodegrading when the researchers examined the plume in June 2010.

"[O]il and gas experienced a significant residence time in the
water column with no opportunity for the release of volatile species into the
atmosphere," the researchers reported.

"Hence water-soluble petroleum compounds dissolved into the water
column to a much greater extent than is typically observed for surface
spills."

"We needed to have an 'end-member' sample, so that we could
compare how nature affected the hydrocarbons as they left the riser pipe,"
Reddy said.

"So this story is really about, 'From pipe to plume: what
chemicals got off the elevator to the surface and migrated to the plume.'"

The findings have "direct implications for the ecotoxicological
impact of plumes," Reddy said. "Now that we know the compounds were
there for a certain time, we need to look at what that would mean to ocean
life. This paves the way to look at any environmental effects."

The key to locating and mapping of the plume and the collection of
samples from the plume was the use of the mass spectrometer TETHYS integrated
into the autonomous underwater vehicle Sentry, funded by NSF.

Developed by Richard Camilli of WHOI's Deep Submergence Laboratory, the
mass spectrometer is capable of identifying minute quantities of petroleum and other
chemical compounds in seawater instantly.

During the June 2010 expedition, Sentry/TETHYS crisscrossed the plume
boundaries continuously 19 times to help determine the trapped plume's size,
shape, and composition.

This knowledge of the plume structure guided the team in collecting
physical samples using a traditional oceanographic tool, a cable-lowered water
sampling system that measures conductivity, temperature, and depth (CTD).

The CTD also was instrumented with a TETHYS the mass spectrometer to
positively identify areas containing petroleum hydrocarbons.

Guided by the Sentry/TETHYS system, the team collected about 100
samples--a painstaking and rigorous process undertaken under strict natural
resource damage assessment (NRDA) protocol and supervision.

Since TETHYS is limited in its ability to analyze petroleum
hydrocarbons, Reddy said, the best samples were brought back to the land-based
laboratories for more sophisticated analyses, which included the help of NOAA.

The current results validated the findings reported with TETHYS, Reddy
said.

Other WHOI researchers who joined Reddy and Camilli in the study were
Sean P. Sylva, Karin L. Lamkau, Robert K. Nelson, Catherine A. Carmichael,
Cameron P. McIntyre, Judith Fenwick, and Benjamin Van Mooy. Also participating
in the study were J. Samuel Arey of the Swiss Federal Institute of Technology
at Lausanne and G. Todd Ventura of OxfordUniversity.
The research was also funded by the U.S. Coast Guard.

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